Poly(difluoramino)alkanes



United States Patent 3,446,847 POLY(DIFLUORAMINO)ALKANES Jeremiah P. Freeman, Huntsville, Ala., assignor to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Filed Sept. 24, 1963, Ser. No. 311,613 Int. Cl. C07c 87/20, 87/22, 85/08 U.S. Cl. 260583 Claims This invention concerns a process for the introduction or difluor'amino groups, NF into organic comp unds, and the NF -containing compounds so produced. More particularly, it concerns the use of enol phosphates which are treated with tetrafiuorohyd'razine, N F and the resulting product is treated with difiuoramine, HNF and sulfuric acid.

This process makes possible the production of poly(difluoramino) compounds which are useful as high energy plasticizers for high energy propellants. Inasmuch as they are high energy compounds, they do not detract from the specific impulse of the propellants prepared therewith, as do other commonly used plasticizers, such as dibutyl phthalate, dioctyl sebacate, dibutyl sebacate, tricresyl phosphate and the like.

The following equations are typical of the reaction steps employed:

0 oiworu); R i R, RCOtitHX P(OR R- H N11. (1) g OP(OR)2 l B2 NF: R2

5 HNF: l RC H RCCH H2304 NF: NF: NF: NF:

(II) (III) in which R=H or lower alkyl, C -C R =lower alkyl, C -C R =H or CH X=Cl or Br Compounds of the general formula (XCH CO) (CH in which X=Cl or Br and 3 :1 to 10, can replace 2 RoodHX in the reactions shown hereinbefore to yield hexakis(difluoramino) compounds.

The equations above represent the reactions which are employed using an a-haloketone to get a tris(difluoramino)-substituted compound. When a di a-haloketone is employed using the same reactions, a hexakis (difluoramino) hydrocarbon is obtained.

The reaction to produce the unsaturated alkyl phos phate (I) is shown in the literature Lichtenthaler, Chem. Rev., 61, 607 (1961). (I)! is converted to a bis(difluoramino) adduct (11) by treatment with N F and this reaction is preferably carried out in an inert solvent such as methylene chloride, ethylene dichloride, carbon tetrachloride, and the like. The reaction is preferably conducted under pressure and this can be in the range from about 1 atm. to about atms. The temperature is in the range 80 C. to 150 C. A particularly preferred range is from 80 C. to 100 C. The molar ratio of the phosphate (I) to the N F can be varied and can be from 1 to 1 to l to 5. A preferred molar ratio is 1 to 3. The reaction of the adduct (II) wdith HNF and H is carried out at a temperature from about 0 C. to 25 C. This reaction is preferably carried out at atmospheric pressure. The molar ratio of the adduct (II) to HNF can be varied from about 1 to 1 to 1 to 5. The preferred molar ratio is from 1 to 3.

The following examples are typical of the reaction of a mono-a-chloroketone and a di-wchloroketone to give a tris (difiuoramino) hydrocarbon and a hexakis(difluoramino) hydrocarbon respectively.

EXAMPLE I Preparation of l,2,2-tris(difiuoramino) propane 1 N2F4 016112000113 (CH3O)3P CH2=CO(OCH3)2 CH3 0 e 1* ENE: NFzCHglOP(OCH3)n E's-0+ NF2CH2C(NF2)2CHI NF! 2 I Isopropenyl dimethyl phosphate (I) was prepared according to literature methods. It was'converted to its N 'F adduct II by heating it under a pressure of 2 atms. in CCL, solution with N F At -80 C. 1.35 g. (0.005 mole) of (II) was added to a mixture of 5 ml. of cone. H 50 and 5 ml. of 30% fuming 'H SO I-INF (225 cc., STP) was admitted and the mixture was stirred at room temperature for an hour. Upon distillation, 1,'2,2-bis(difluoramino) propane was obtained.

Calcd: C, 18.3; H, 2.5; N, 21.3; F, 57.9. Found: C, 18.0; H, 2.7; N, 20.8; F, 56.8.

* EXAMPLE 11 Preparation of l,2,2,7,7,8-hexakis(difluoramino) octane ClCHzCOCHaCHaCHzCHzCOCHzCI 2(CH3O)3P i IV lNrFl This bis-enol phosphate (IV) was prepared as shown in the equation. It was characterized by its infrared spectrum. Its N F adduct was prepared in the usual way and characterized by infrared and n.m.r. spectra.

To 1.35 g. (0.0025 mole) of (II) in 10 ml. of H 80 was added 450 cc. (STP) of HNF This mixture was stirred at room temperature for an hour. It was then poured into water and extracted with methylene chloride. The desired hexakis(difiuoramino) octane was obtained by evaporation.

Analysis.Calcd for C H N F C, 22.75; H, 3.34; N, 19.91; F, 54.00. Found: C, 22.91; H, 3.70; N, 20.06; F, 54.10.

I claim:

1. A method for the preparation of poly(difiuoramino) compounds which comprises reacting a member from the class consisting of R2 R 0 o JHX and (XCH CO) (CH y with a compound having the formula P(OR followed by reaction with tetrafiuorohydrazine, and finally with difiuoramine in the presence of sulfuric acid in which R is selected from the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms, R is alkyl of 1 to 4 carbon atoms, R is selected from the group consisting of hydrogen and methyl, X is selected from the group consisting of chlorine and bromine, and Y is an integer of 1 to 10.

2. A method according to claim 1 wherein the reaction with tetrafluorohydrazine is conducted at a temperature of about80" to about 150 C. at a pressure of about 1 atmosphere to about 25 atmospheres, in which the reaction with difiuoramine is conducted at a temperature of about 0 to 25 C. at atmospheric pressure.

3. A composition of matter selected from the group consisting of those compounds having the formula I IFz I IFZ in which R is selected from the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms, and R is selected from the group consisting of hydrogen and methyl, and

in which y is an integer of 1 to 10.

4. 1,2,2-tris(difluoramino) propane. 5. 1,2,2,7,7,8-hexakis(difluoramino) octane.

References Cited UNITED STATES PATENTS 

1. A METHOD FOR THE PREPARATION OF POLY (DIFLUORAMINO) COMPOUNDS WHICH COMPRISES REACTING A MEMBER FROM THE CLASS CONSISTING OF
 3. A COMPOSITION OF MATTER SELECTED FROM THE GROUP CONSISTING OF THOSE COMPOUNDS HAVING THE FORMULA 